DE3511513A1 - POLYOLEFINS WITH BRANCHED ALKYL SIDE CHAINS - Google Patents

Description

D 7270
"Polyolefins with unbranched alkyl side chains"

; The invention relates to oil-soluble polyolefins based on polybutadienes, which are ^{replaces them} by epoxidation and subsequent ring opening with long-chain carboxylic acids, long-chain alcohols and, if desired, modifiers for polymers with alkyl side chains unbranched chain length ^c i2 ~ ^C 24 ^UIIl. 9 The products are suitable as flow improvers for paraffin-containing crude oils.

In the course of the shortage of crude oil are in increasing Measures oils promoted and processed that have a relatively high proportion of paraffinic hydrocarbons, which are involved Are solid at room temperature. Such oils lose their flowability when cooling down from the increased deposit temperature to room temperature due to the crystallization of components with a higher melting point. In order to avoid difficulties in extraction, transport and processing, one therefore uses crude oil in a still warning state, as it occurs at the borehole, i.e. in a state in which the paraffin is still in the Crude oil is dissolved, so-called fluidity improvers, also crystallization inhibitors (flow improvers) called, too. As a rule, these are polymers. They prevent education larger paraffin crystal associations and thereby cause an improvement in the flowability of the crude oil. this goes hand in hand with a reduction in the so-called pour point. The pour point is the temperature at

Patent application D 7270

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Henkel KGaA ZR-FE / patents

which the crude oil according to a standard method
has defined flow state. Accordingly
are usually also flow improvers
Called pour point depressants and characterized by the pour point depression made possible.

A number of such products are already known; so in the German Offenlegungsschrift 22 64 328, the use of polymeric acrylic esters with 18 to 24 carbon atoms in the alcohol radical. The relatively high concentrations used are a disadvantage from 0.01 to 3% by weight based on petroleum. Another The disadvantage is that the stock solutions themselves Flow improvers, usually 30 to 50% solutions in toluene at temperatures around freezing point or below, is difficult or impossible to handle.

This disadvantage also applies to the products named in German Offenlegungsschrift 32 26 262. These are esters of (meth) acrylic acid with long-chain alcohols, which have been chain-extended by reaction with ethylene oxide and / or propylene oxide. Although these products lower the pour point even in very small amounts, their solutions are below about 0 at temperatures
still workable.

C hardly

Reaction products of epoxidized polybutadienes are on; already known in other areas of technology and in j Mission. Thus, in the not previously published j

j German patent application, file number: I

'P 34 42 200.5 describes air-drying lacquer binders, which are Uir.setzungprodukte epoxidized

Patent application D 7270 -T "" - Henkel KGaA

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Polybutadienes with unsaturated carboxylic acids or with Alcohols of functionality 2 to 6 are, in a subsequent step by esterification with unsaturated Carboxylic acids with 6 to 22 carbon atoms up to an OK number of less than 10 have been implemented. A ; The advantage of these products lies in addition to the paintwork

desired drying properties in the low; Viscosity compared to polymers of the same molecular weight and other construction. Due to this low viscosity, such products have the advantage that they can be prepared solvent-free and therefore in a solvent of choice before use can be brought into solution. In contrast, pour point depressants based on (meth) Acrylic esters common to produce the monomers by azeotropic esterification in toluene or xylene and in also polymerize this solvent.

It is therefore an object of the invention, starting from epoxidized Polybutadienes to create new polyolefins with unbranched alkyl side chains, their alkyl side chains are at least predominantly saturated. Another object of the invention is in Shape of these polyolefins with unbranched alkyl side chains new pour point depressants are available which are in a simple manner in substance i.e.

Can be produced solvent-free and to; Stock solutions that can be processed by themselves

I can still be dosed ^{by 0 0 C.}

■ The invention is thus

Patent application D727O - · * Γ - Henkel KGaA

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Polyolefins with unbranched alkyl side chains of chain length ^c i2 * " ^C 24 'produced by reacting epoxidized polybutadienes with long-chain alcohols or carboxylic acids and, if desired, modifiers, characterized in that they are ring opening products

a polymer based on butadiene with epoxy groups and, if desired, double bonds on the one hand
and from

Saturated carboxylic acid mixtures with CJ ₂ -C ₂₄ C atoms, which, if desired, can be replaced by short-chain carboxylic acids up to 30 mol%
and or

saturated primary alcohols with 12 to 24 carbon atoms and / or

On the other hand, alcohols of functionality 2 to 6

those with saturated carboxylic acid mixtures with 12 up to 24 carbon atoms are esterified to an OH number of less than 20.

According to the invention, under polybutadiene, the first

understood different structural isomeric homopolymers of 1,3-butadiene. However, the term also includes; '. those copolymers in which butadiene is decisive for the chemical character of the compound. The homopolymers of butadiene can exist in two isomers, namely as 1,4-polybutadiene and as 1,2-polybutadiene. 1,4-Polybutadicne are linear,

[^ SPECTED

Patent application D 7270-5 "- Henkel KGaA

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[unbranched configured and contained in the main chain double bonds, the "ice", or "trans" can. The 1,2-polybutadienes contain side groups with a vinylic double bond.

As starting materials for the erfindungsgeraektiven Polyolefins with unbranched alkyl side chains are the epoxidation products of all of the isomers mentioned suitable.

| According to a first embodiment of the invention can for example partially epoxidized cis-1,4-polybutadienes' can be used. For example, 1,4-polybutadienes with more i suitable as 70% cis-configured double bonds. Such products with 80 or even 98% cis-configured double bonds that are available in stores.

According to a further embodiment of the invention, 1,4-polybutadienes can also be used which contain more than 20, in particular more than 50% trans double bonds have, e.g. products with 60 to 98% trans double bonds.

Another embodiment relates to poly-1,2-butadienes, i.e. materials with vinylic double bonds. A very suitable starting material is a product with more than 80 or more than 90% lateral double bonds, i.e. 20-98% lateral double bonds.

In the majority of cases, the person skilled in the art will use a mixture of isomers of polybutadienes, that is to say about 1,4-polybutadienes with 20 - 70% cis double bonds and / -

Patent application D727O - ^ i- Henkel KGaA

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or 20 - 50% trans-permanent double bonds, the next also 0 - 3%, 3 - 30% or even more
Have side groups with vinylic double bonds
can. Regarding the producibility of polybutadienes
the general applies with different configurations
Expertise in polymer chemistry, reference is made, for example, to the monograph "Macromolecules" by HG Elias,
4th edition, Hüthig and Wepf-Verlag, Basel, Heidelberg,
New York, pages 676 (configuration change "eis" to
"trans") as well as pp. 744-746 and 1012 ff.

'The polyolefins according to the invention with unbranched
. In addition to epoxidized homo-

ί j

polymers of 1,3-butadiene also from epoxidized;

Copolymers are produced. Suitable copolymers
are copolymers of butadiene and styrene, copolymers
: made of butadiene and acrylonitrile as well as copolymers made of

Butadiene, styrene and acrylonitrile. In any case, should
■ the butadiene content is not less than 50 percent by weight
! lie.

In any case, the epoxidation process is after

I!

i the epoxidized on which the polyolefins are based

j I

i Polybutadienes have been produced, little critical. .

; All technically customary epoxidation measures can be used ^:

j are carried out e.g. epoxidation with peracids j

25 like peracetic acid.

Although the polyolefins according to the invention with unbranched alkyl side chains are epoxidized polybutadienes! with 1 to 8 percent by weight of epoxy oxygen
it is preferred to be epoxidized

Patent application D 727O - • Τ'- Henkel KGaA

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To use polybutadienes with 2 to 6 and in particular 3 to 5 percent by weight of epoxy oxygen. Per 100 originally present double bonds can thus cause up to 50% or less of the epoxidation be subjected. The stated percentages relate to polybutadiene. In the case of copolymers of In terms of double bonds, butadiene is an essential

^! Set a correspondingly higher degree of conversion in order to keep the total epoxy oxygen content between 1 and 8%. For the properties of the polyolefins according to the invention with unbranched alkyl side chains, the molecular weight is of minor importance.

, This property has at most an influence on the viscosity of the stock solutions. It can therefore be under the aspects of pourability and processability, especially desired at low temperatures be more likely to use products with a lower molecular weight. Polyolefins according to the invention with unbranched Alkyl side chains are therefore preferably derived from epoxidized polybutadiene with a molecular

! weight from 500 to 10,000. These have products with an average molecular weight of 500 to 5000 and in particular from 1000 to 2000 particularly favorable properties.

The polyolefins according to the invention with unbranched alkyl side chains contain in each case side chains to 24 carbon atoms \ derived from carboxylic acids by 12. The carboxylic acid residues go to saturated carboxylic acids or saturated carboxylic acid

30, mixes back. Particularly suitable

Carboxylic acid mixtures are fatty acids. Fatty acids are understood as meaning mixtures of monofunctional carboxylic acids with an even number of carbon atoms, which are derived from natural oils and fats. Before-

Patent application D 7270

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Fatty acids with 16 to 22 carbon atoms, i.e. palmitic acid, stearic acid, arachidic acid or behenic acid are preferred. In minor amounts, unsaturated, in particular olefinically simple or polyunsaturated fatty acids are also used. Subordinate quantities are to be understood here as that the fatty acids themselves have an iodine number of less than 50 and in particular less than 10. They are therefore mixtures of fatty acids preferred which have been subjected to a catalytic hydrogenation or partial hydrogenation. For example, hardened tallow fatty acid, hardened rapeseed oil fatty acid or, for example, hardened soybean oil fatty acid can be used, but generally other hydrogenated fatty acids from vegetable, animal or marine fats are suitable, provided they are at least predominantly made up of carboxylic acids with 12 to 24 carbon atoms exist.

The carboxylic acids mentioned with 12 to 24 carbon atoms can be converted into polyolefins with unbranched alkyl soite chains have been introduced as part of the ring opening reaction, in addition, they are in the second reaction step by reaction with the secondary hydroxyl groups (Post-esterification) introduced. To modify the polyolefins according to the invention with unbranched However, alkyl side chains can also contain up to 30 mol% short-chain monocarboxylic acids with 4 to 10 carbon atoms are used. Both linear ones are suitable here as well as branched monocarboxylic acids, for example isobutyric acid, cyclohexanecarboxylic acid or benzoic acid. Short-chain fatty acid cuts with up to 10 carbon atoms can also be used.

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Patent application D 7270 - ^ - HENKELKGaA

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The olefins according to the invention with unbranched alkyl chain sides contain the monocarboxylic acids, either directly via ester groups to the polybutadiene skeleton bound or via an intermediate group derived from a polyfunctional alcohol. Than more-. functional alcohols are here aliphatic alcohols'; suitable for functionality 2 to 6, which have 2-12 carbon atoms and up to 3 ether oxygen atoms may contain. Thus, as difunctional alcohols, for example those customary in the paint industry Diols such as ethylene glycol, propylene glycol, neopentyl glycol or their di- and trimers with 2 or 3 Ether-oxygen bridges are used in the molecule. Suitable triols are glycerol, trimethylolethane, trimethylolpropane. Suitable alcohols of functionality 4 are, for example, pentaerythritol or the dimers of the aforementioned triols. An aliphatic alcohol with OH groups is, for example, sorbitan, but the trimers of the aforementioned triols are also suitable here with 2 ether-oxygen bridges in the molecule.

When selecting the alcohols of functionality 2 to 4 used for ring opening, aliphatic alcohols are used preferred. In any case, the person skilled in the art must ensure that there is sufficient solubility in polybutadienes given is. This is, for example, in the case of the preferred polyhydric alcohols trimethylolpropane, Ditrimethylolpropane and glycerin the case.

According to a further embodiment of the invention, reaction products of epoxidized polybutadienes in which the epoxy group has been opened with primary linear alcohols of chain length ^c 12 ~ ^C 24 9 ^{e are also} suitable. Among the monofunctional ones possible here

Or ^ mu. fMSPECTED

File number: ι ³ 35 11 513.0 ": changed page 10.:,

FOLLOW-UP

Patent application D 7270

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Primary, linear alcohols are particularly suitable fatty alcohols, the fatty alcohols corresponding to the aforementioned fatty acids being preferred. The ring opening can be carried out with lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, arachidyl alcohol or behenyl alcohol or mixtures thereof, which can be produced from fatty acids by hydrogenation of the carbonyl function and possible double bonds. Among the mentioned fatty alcohols are fatty alcohols of chain length C ₁ O and C ₃₃ particularly favorable and preferred modifying agent. This also applies to the corresponding fatty acids.

For the preparation of polyolefins having unverzv / eigten alkyl side chains is assumed epoxidized Polybutadicnen and these eigten with the saturated carboxylic acid mixtures, or with the long-chain primary unverzv / alcohols of chain length C-2 "" C * ^ ⁿ reacted a first stage. Are products to be manufactured, which between the polybutadiene base. body and the saturated carboxylic acid residues an intermediate

; member based on one of the multifunctional ones mentioned above contain aliphatic alcohols, or those with primary, monofunctional, long-chain alcohols are modified, the epoxidized polybutadienes are first reacted with the corresponding alcohols. The alcohol-modified polybutadienes are then esterified with the saturated carboxylic acid mixtures. The reaction of polybutadienes with saturated carboxylic acids takes place at temperatures between 200 and 250, preferably at 230 instead. Conveniently will

ORfCBf

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the reaction was carried out under inert gas (nitrogen). Customary catalysts suitable for converting epoxides can be used here. Suitable catalysts are, for example, organometallic compounds of the elements tin or titanium. Organotin compounds are particularly suitable, for example acidic organotin compounds.

A catalyst with the trade name Swedcat 3 from Swedstab-AB, which is an acidic organotin compound, is particularly suitable. The reaction can be carried out in bulk or in a suitable solvent. Suitable solvents are high-boiling hydrocarbons such as xylene. Up to 2 moles of fatty acids can be used per mole of epoxide groups. It has proven to be advantageous to use more than 1 mol but less than 2 mol of fatty acids, for example 1.7-1.9 mol of fatty acid per mole of epoxy groups, taking into account the alcohols used for ring opening, the usual reaction time of the reaction is between 2 and 12 hours depending on the catalyst and temperature. It has been shown that with a molar deficit of 15 to 20 Z, based on the equivalence of 2 mol of fatty acid per mol of epoxy group, products are obtained which have both a low OH number and a low acid number, whereas the direct one Equivalence more or less large amounts of carboxylic acid groups remain and in this way create a disruptive acid number.

For the production of polyolefins according to the invention with unbranched alkyl side chains that are either long-chain primary alcohol residues or polyfunctional alcohols as a bridge between polybutadiene and

File number: P 35 11 573.Ώ, I ::. ".. *: .- ι

modified page 12 .J _J * \ ^{"Γ *: ..:} ... * j NAOHQERBOHT |

Patent application D 7270-4-2 "- Henkel KGaA

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contain the saturated carboxylic acid mixtures epoxidized polybutadienes first reacted with the alcohol component. :

The reaction can be carried out with bases such as alkali or alkaline earth hydroxides or tertiary amines are catalyzed. The reaction temperatures are between 150 and 200 °, in particular between 160 and 180 °, the reaction times being in the range of a few hours. Around To get particularly cheap products, it is

10 ser reaction displayed, the catalyst and the

Submit polyfunctional alcohol in the reaction vessel and the epoxidized polybutadiene in the course of the reaction as such or in solution to be added continuously or in portions. To remove the basic catalyst this can be neutralized with acids, for example HCl, and then separated off by hot filtration. The compounds containing hydroxyl groups and based on polybutadienes that are prepared in this way are mixed with unsaturated ones Monocarboxylic acids esterified exhaustively until the OH number is below 25, preferably below 15 or especially below 10 has fallen. The esterification can be catalyzed in a customary manner. So here too, for example Organotin compounds or organotitanium compounds, especially acidic organotin compounds

25 can be used.

The aim of the products according to the invention is to keep the OH number below 20 and preferably below 10 mg of the KOII program. The acid number should also be below 20 and preferably below 10 mg KOH per gram. Products which can be assessed as being favorable are obtained when the conversion ratio (per mol) of fatty acid to epoxide is between 1 ^: 1 and 2 ^: 1, preferably 1.3: 1 and

ORIGINAL

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1.8: 1, or if the conversion ratio is fatty alcohol to epoxy is 0.8: 1 to 1.2: 1, preferably 0.9: 1 to 1.1: 1. The total molecular weight is (Number average) 1,500 to 10,000, in particular 2,500 to 7,000.

Pour point depressants, judged to be particularly favorable, are also derived from saturated carboxylic acids 18 and with 22 carbon atoms or from the corresponding fatty alcohols. Because of the relatively low viscosity of the polymers, it is possible to carry out the reaction, i.e. both the ring opening and the To carry out esterification in the melt. The melts obtained in this way can after cooling or in the Heat can be diluted with any non-polar solvent. The same for other products due to the manufacturing method given need to rely on such solvents to limit which form a low-boiling azeotrope with water. It is therefore preferred that the to offer pour point depressants according to the invention as solutions in high-boiling hydrocarbons. A Another advantage of the products is the low viscosity of such solutions, their low pour point and in the simple way in which the products are manufactured.

The amount used of the pour point depressants according to the invention is from 20 to 400 ppm, preferably from 40 to 200 ppm based on mineral oil.

Patent application D 7270 - tf - HENKELKGaA

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Examples Example 1

The properties of the epoxidized polybutadienes used are listed in Table 1:

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No. Trade name
(Manufacturer) Wt .-% epoxy
oxygen ice 1 Iso
, 4 mers distribution
trans 1.4 40 uhg (%)
1.2 (vinyl) Molge "
v / i ch t 1 . Lithene PM epox. (Chemetall) 3.2 15 - 25th 30 - 50 1500 2. Poly-bd R45HT epox.
(Chemetall) 6.15 60 20th 20th 2800 3. Poly oil sleeve 110 epox. (CVJH) 8.6 75 24 1 1500 4th Nissin BF 1000 resin
(Nippon Soda) 7.2 < 15 ^ 15 40 > 85 1000 5. Lithene PM epox. (Chemetall) 3.4 15 - 25th 30 - 40 50 1500 6th Lithene PM epox. (Chemetall) 4.7 15 - 25th 30 - 50 1500 7th Poly oil sleeve 110 epox. (CWH) 4.4 75 24 1 1500 8th. Poly oil sleeve 110 epox. (CWH) 3, I. 75 24 1 1500

Patent application D 7270 ~ \ ßr - HENKELKGaA

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Example 2

Conversion of epoxidized polybutadienes with fatty acids

In a standard laboratory apparatus consisting of a three-necked round bottom flask, stirrer, thermometer, water separator and reflux condenser were mixed:

5 250 g (0.5 "mol") epox. Polybutadiene No. 1

(Example 1) 274 g of hardened rapeseed oil fatty acid

(Composition: 4% palmitic acid, 44% stearic acid, 2% oleic acid, 8% arachidic acid, 42% behenic acid)

1 g Swedcat 3 catalyst (Swedstab AB)

(acidic organotin compound) 100 ml xylene

The batch was heated up, and so much xylene was distilled off until the temperature was set at 230 to 240 ^° C. 7 ml of condensate (water of reaction) were deposited azeotropically. The solvent was then removed by vacuum distillation. The total reaction time was 6 to 8 hours, the acid number of the waxy, soft product was 7.9 mg KOH per gram.

Example 3

Example 2 was repeated except that 235 g of epoxidized polybutadiene No. 5 and 259 g of that in Example 2 were used Hardened rapeseed oil fatty acid described is used. The acid number (AN) was 6.5.

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Patent application T) 7270 - Xl · - HENKELKGaA

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• 34-

Example 4

200 g epox. Polybutadiene Mr. 2 42Og hardened. Rapeseed oil fatty acid SZ 8.7

100 g epox. Polybutadiene No. 3 295 g hardened. Rapeseed oil fatty acid

SZ 7.2

Example 6

200 g epox. Polybutadiene No. 6 250 g stearic acid

SZ 5.4

Example 7

100 g epox. Polybutadiene No. 4 261 grams of behenic acid

SZ 6.8

Example 8

200 g epox. Polybutadiene No. 7 213 g tallow fatty acid

SZ 7.6

Patent application D 7270 - * β "- HENKELKGaA

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Example 9

Implementation of epoxidized polybutadienes with polyfunctional alcohols. It was in the example 2 Laboratory apparatus described worked. The following were used:

272.5 grams of dimeric trimethylol propane

4 _f 5 g potassium hydroxide (5 mol% based on

Epoxy oxygen)

400 g of epoxidized polybutadiene No. 400 ml of diethylene glycol dimethyl ether

The dimeric trimethylolpropane was used to carry out the reaction and the potassium hydroxide placed in the reaction vessel - it was then the epoxidized polybutadiene dissolved in diethylene glycol methyl ether and 6

Maintained 1 5 hours at the boiling temperature of the reaction mixture (165-175 ⁰ C). After neutralization with hydrochloric acid, the mixture was filtered hot. The solvent was distilled off in vacuo at a maximum temperature of 17O ⁰ C. The end product had an OH number of 314, the epoxy

oxygen level had fallen below 0.1.

Example 10

The procedure was as in Example 8, were used:

50 g epoxidized polybutadiene No.

23 g of dimeric trimethylol propane

140 g of diethylene glycol dimethyl ether and

0.5 g potassium hydroxide

The OH number was 237.2.

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Patent application D 7270 -W- HENKELKGaA

ZR-FE / patents Example 11

The esterification of the products of the conversion of epoxidized polybutadienes with polyfunctional alcohols was used Proceed in analogy to Example 2. Were used:

5 150 g of reaction product from Example 9

(OHZ 314)
272 g of hardened rapeseed oil fatty acid

1 g of Swedcat 3 catalyst, 50 ml of xylene

The maximum temperature was 240 ^° C. and the reaction time was 7 hours. 15 ml of water of reaction were separated off and the solvent was then distilled off in vacuo. The product had an acid number of 2.6 mg KOH per gram.

15 Example 12

There were mixed:

200 g epox. Polybutadiene No. 1

7 g isobutyric acid

168 g hardened rapeseed oil fatty acid

20 1g catalyst Swedcat 3

^{The batch was stirred at 230 to 240 °} C. for 8 h under a gentle stream of nitrogen. A vacuum of approx. 100 hPa (30 min) was then applied at this temperature. The acid number of the product obtained was 7.6 mg KOH per gram.

Patent application D 7270 - 2Cf - HENKELKGaA

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Example 1 3

Conversion of epoxidized polybutadienes with fatty alcohols.

Were used:

5 300 g epoxidized polybutadiene Kr. 8 176 g C ₁₈ / C22 ~ ^{fatty alcohol} 9 ^{em: i} - ^sch 1.7 g potassium hydroxide

To carry out the reaction, the components were mixed, ^{heated to 180 °} C. within 1 h and kept at this temperature for 7 h. After cooling to about 90 ^° C., the mixture was neutralized with acetic acid and cooled to RT. The end product had an OH number of 61, the epoxy oxygen content had fallen below 0.1.

15 Example 14

Conversion of epoxidized polybutadienes with fatty alcohols and further conversion with fatty acids

Were used:

250 g epoxidized polybutadiene # 5

20,160 g o C ₁ / C ₂ 2 ~ ^{Fet 'talkonol emiscn} g 1.6 g of potassium hydroxide

The reaction took place as in Example 13. The product obtained with OHN 65 was further esterified directly: The following were added to the neutralized batch:

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Patent application D 7270 - 2A- - HENKELKGaA

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77 g hardened rapeseed oil fatty acid 1.5 g Swedcat 3 100 ml of xylene

The esterification was carried out as described in Example 2. The acid number of the product obtained was 2.8, the hydroxyl number 19.

Example 15 Test for flow-improving effect

To test for flow-improving effect, solutions of paraffin with a solidification point of 46 to 48 ° C in gasoline with a boiling point of 145 to 200 ° C. The paraffin content was 15 percent by weight. The solutions were mixed with 100 ppm of the new products and cooled until they solidified and during thawing, the temperature at which the solidified mixture became liquid is determined. Reference product was a commercially available flow improver.

example Pour point (without addition: 15 ° C) 2 1 ° 3 1 ° 4th 2 ° 5 2.5 ° 6th 6 ° 7th 4.5 ° 8th - 11th 1.5 ° 12th 1 ° 13th 0 ° 14th 1 ° • · ·

3611513

Patent application D 7270 - QA - HENKELKGaA

ZR-FE / patents Special advantages

A particular advantage of the new products is the relatively low pour point of 50% solutions in toluene (^ O ⁰ C) customary in practice.

A further advantage is the possibility of strength for producing the solutions of 50% less hazardous solvent, such that with a higher flashpoint to use (for example Solvesso ^ 200, Flash point> 100 ⁰ C).

Such solutions can be made

(i) by the reaction already in a corresponding Solvent is carried out,

(ii) by making the products in the melt and dissolving the products after the reaction in an appropriate solvent.

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Claims (1)

Claims 'Polyolefins with unbranched alkyl side chains ι chain length ^c -j2 ~ ^C 24' produced by reaction of epoxidized polybutadienes with long-chain alcohols or carboxylic acids and, if desired, modifiers, characterized in that they are ring-opening products! ; negotiates a polymer based on butadiene with epoxy groups and, if desired, double bonds on the one hand
and from Saturated carboxylic acid mixtures with C ₁₃ -C ₃₄ carbon atoms, which, if desired, can be replaced by up to 30 mol% by short-chain carboxylic acids ^! can
and or saturated primary alcohols with 12 to 24 carbon atoms
and or On the other hand, alcohols of functionality 2 to 6 those with saturated carboxylic acid mixtures with 12 to 24 carbon atoms up to an OK number less than 20 are esterified. 2. Polyolefins with unbranched alkyl side chains j according to claim 1, characterized in that it j in the epoxidized butadiene is a 1,4-polybutadiene with more than 20, in particular more acts as 70% cis double bonds. Patent application D 7270 'λ. Henkel KGaA ZR-FE / patents 3. Polyolefins with unbranched alkyl side chains according to claim 1, characterized in that it the epoxidized polybutadiene is 1.4 polybutadiene with more than 20, in particular more than 50% trans double bonds are involved. j 4. polyolefins with unbranched alkyl side chains j according to claim 1, characterized in that it the epoxidized polybutadiene is a polymer with 20 to 98% pendant groups Double bonds. Polyolefins with unbranched alkyl side chains according to Claim 1, characterized in that it The epoxidized polybutadiene is an epoxidized copolymer of butadiene, styrene and if desired, acrylonitrile with a butadiene content of not less than 50 percent by weight. ! 6. Polyolefins with unbranched alkyl side chains ! according to claims 1 to 5, characterized in that ι that the epoxidized polybutadiene has a molecular weight (Number average) from 500 to 10,000, in particular from 1000 to 2000. 7. Polyolefins with unbranched alkyl side chains according to Claims 1 to 6, characterized in that ι that the epoxidized polybutadienes have an epoxy oxygen content of 1 to 8 percent by weight, ! preferably from 2 to 6 percent by weight and in particular from 3 to 5 percent by weight. Patent application D 7270-23 "- Henkel KGaA ZR-FE / patents Polyolefins with unbranched alkyl side chains according to claims 1 to 7, characterized in that the saturated carboxylic acid mixtures are about fatty acids with an iodine number less than 50, in particular less than 10 and preferably 16 up to 22 carbon atoms. j 9. Polyolefins with unbranched alkyl side chains ■ according to claims 1 to 8, characterized ' Not that it is with the carboxylic acid mixtures ! to hydrogenated fatty acids from vegetable, animal i see or trade marine oils, especially hardened tallow fatty acid and / or : hardened rapeseed oil fatty acid. j 10. Polyolefins with unbranched alkyl side chains l according to claims 1 to 9, characterized marked- [ net that the carboxylic acid mixtures up to 30 mol% j short-chain carboxylic acids, in particular monocarboxylic '■ acids with 4 to 10 carbon atoms, which also branched 20; or can be aromatic. : 11. Polyolefins with unbranched alkyl side chains ! according to claims 1 to 10, characterized in that the alkyl side chains are from fatty alcohols j with 12 to 24 carbon atoms, in particular derived from stearyl alcohol (C ₁₈ ) or behenyl alcohol (C ₂₂ ). 12. Polyolefins with unbranched alkyl side chains according to claims 1 to 11, thereby marked ^! net that the alcohols of functionality 2 to 6 aliphatic alcohols with 2 to 12 carbon atoms and up to 3 ether oxygen atoms are included. File number: P 35 11 "513 ^ 0 changed page 26 -. ... * 513 Patent application D 7270 - err - Henkel KGaA ZR-FE / patents 13. Polyolefins with unbranched alkyl side chains according to claims 1 to 12, characterized in that the polyfunctional alcohols are diols, in particular ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol; Triplets, in particular Glycerol, trimethylolethane, trimethylolpropane or tetraols, in particular pentaerythritol, ditrimethylolethane or ditrimethylolpropane are present. . 14. Polyolefins with unbranched alkyl side chains according to claims 1 to 13, characterized in that the total molecular weight (on numbers-I medium) 1500 to 10,000, especially 2500 to! 7000 is. ; 15. Process for the production of polyolefins with j unbranched alkyl side chains according to the i Proverbs 1 to 14, characterized in that ^! an epoxidized polybutadiene with monofunctional ! Carboxylic acids with 12 to 24 carbon atoms or primary Alcohols of the same chain length or with Al- I alcohol functionality 2 to 6 of the complete i is subjected to ring opening and then the ι resulting polyol with the same or different I saturated carboxylic acids up to a radical OH- : Number less than 20 is esterified. 16. Use of the polyolefins with unbranched alkyl side chains according to Claims 1 to 15 as a pour point depressant for paraffin and / or! waxy hydrocarbons, in particular . Mineral oil in amounts of 20 to 400, preferably 40 to 200 ppm. ! GRlGIiUL KSi